US3334982A - Manufacture of silica glass - Google Patents

Manufacture of silica glass Download PDF

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Publication number
US3334982A
US3334982A US169763A US16976362A US3334982A US 3334982 A US3334982 A US 3334982A US 169763 A US169763 A US 169763A US 16976362 A US16976362 A US 16976362A US 3334982 A US3334982 A US 3334982A
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United States
Prior art keywords
hydrogen
chlorine
oxygen
silica glass
vapors
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US169763A
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English (en)
Inventor
Mattmuller Rene
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie de Saint Gobain SA
Original Assignee
Compagnie de Saint Gobain SA
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Publication date
Application filed by Compagnie de Saint Gobain SA filed Critical Compagnie de Saint Gobain SA
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Publication of US3334982A publication Critical patent/US3334982A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
    • C03B19/1415—Reactant delivery systems
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/32—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/50—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with alkali metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/04—Multi-nested ports
    • C03B2207/06—Concentric circular ports
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/20—Specific substances in specified ports, e.g. all gas flows specified
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/20—Specific substances in specified ports, e.g. all gas flows specified
    • C03B2207/26—Multiple ports for glass precursor
    • C03B2207/28—Multiple ports for glass precursor for different glass precursors, reactants or modifiers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/36—Fuel or oxidant details, e.g. flow rate, flow rate ratio, fuel additives
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/46—Comprising performance enhancing means, e.g. electrostatic charge or built-in heater
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/80—Feeding the burner or the burner-heated deposition site
    • C03B2207/81—Constructional details of the feed line, e.g. heating, insulation, material, manifolds, filters
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/80—Feeding the burner or the burner-heated deposition site
    • C03B2207/85—Feeding the burner or the burner-heated deposition site with vapour generated from liquid glass precursors, e.g. directly by heating the liquid
    • C03B2207/86—Feeding the burner or the burner-heated deposition site with vapour generated from liquid glass precursors, e.g. directly by heating the liquid by bubbling a gas through the liquid
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/80—Feeding the burner or the burner-heated deposition site
    • C03B2207/85—Feeding the burner or the burner-heated deposition site with vapour generated from liquid glass precursors, e.g. directly by heating the liquid
    • C03B2207/87—Controlling the temperature
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/80—Feeding the burner or the burner-heated deposition site
    • C03B2207/90—Feeding the burner or the burner-heated deposition site with vapour generated from solid glass precursors, i.e. by sublimation

Definitions

  • This invention relates to the manufacture of silica glass by the decomposition of the vapors of a silicon hallde, such as silicon tetrachloride, in the flame of an oxyhydrogen blowpipe and the vitrification of the silica collected on a support.
  • a silicon hallde such as silicon tetrachloride
  • the silicon halide is entrained in the oxygen which supplies the blowpipe, but this is imperfect in that amorphous silica forms on and restricts the discharge orifice of the burner.
  • an inert gas for instance nitrogen or argon
  • the oxygen loaded with vapors of silicon halide and the hydrogen so as to produce a gaseous screen preventing the oxhydric reaction at the output of the burner and to transport the flame beyond the burner and prevent the accumulation on the burner, but the inert gas chills the flame and reduces the yield.
  • oxygen has also been suggested to interpose between the oxygen loaded with halide vapors and the hydrogen, oxygen free from halide vapors in place of the inert gas.
  • the flame is in this case not separated from the burner but the decomposition of the silicon halide vapors is slightly retarded sufficiently to avoid the collection of amorphous silica on the burner and therefore prevent the restriction of the discharge orifice.
  • the apparatus must however provide an additional oxygen input and becomes complex. Moreover if oxygen will entrain SiCl this is not the case for several other silicon halides.
  • the objects of the invention are to improve the manufacture of silica glass by vapor phase reactions utilizing the blowpipe process, to prevent accumulations on the burner orifice, and ameliorate the operation of the blowpipe.
  • the objects are accomplished, generally speaking, by a method of preparing silica glass that comprises entraining a silicon halide in a current of halogen gas, bringing the current together with a current of hydrogen and a current of oxygen, igniting them, and condensing the glass formed on a cold surface.
  • a major feature of this invention' is the use of a halogen gas to entrain the silicon halide vapors.
  • a major advantage is the complete elimination of the difficulties that plagued the prior art. The operation of the blowpipe is improved and the formation of accumulations is ended.
  • the most advantageous halogen for the entrainment of the silicon halide is chlorine.
  • the chlorine stabilizes the silicon halide vapors, which do not decompose even as they enter the flame.
  • the chlorine reacts with hydrogen exothermically and the flame suffers no cooling.
  • chips of metals can be introduced directly into the evaporation container instead of handling silicon halides several of which, being hydrolyzable and generating fumes, decompose in air.
  • the blowpipe is shown in vertical section in the drawing and may conveniently be comprised of three concentric tubes, of which the central receives silicon halide in a stream of halogen gas, particularly chlorine, the intermediate tube receives oxygen, and the outer receives hydrogen.
  • the silica or glass formed in the flameblown from the blowpipe is directed upon a cold support, which may be a refractory rod moving endwise through the flame as it is rotated about its axis and is separated from said support after cooling by means of a millstone.
  • the invention may produce pure silica glass containing United States Patent 0 3,334,982 Patented Aug. 8, 1967 to Si0 or it may produce silica glass containing otheringredients such as germanium oxide, alumina, titatnium dioxide, ferric oxide, either separately or simultaneously for several of them, with various concentrations.
  • These ingredients may be entrained either by one of the gases or by both the halogen and the hydrogen. For instance, sodium and other alkali metals may be entrained in the hydrogen, and aluminum chloride may be entrained with the silicon chloride in the halogen gas stream. These added ingredients are most frequently present in about 5 weight percent of the glass. This simultaneouse entrainment of different ingredients by the hydrogen and the halogen streams is advantageous in making the more complex glasses.
  • the decomposition products are heated to a temperature at which the vapor tension is suflicicnt to produce an adequate entrainment.
  • SiCl need only be brought to room temperature and chlorine is allowed to bubble in the SiCL, vapors.
  • Aluminum chloride may be heated to 90 C. and the vapors are leached by a chlorine stream.
  • the pipings conducting the vapors are heated only if necessary to obviate condensation. Accordingly no heating is necessary with SiCl
  • the pipings may be heated up to about 200 C.
  • Oxygen may be heated at the same temperatures as those of the vapors utilized.
  • the drawing is a schematic view of the invention in operation, the blowpipe being comprised of three concentric tubes 10, 11, 12.
  • a stream of chlorine gas which has been bubbled through liquid SiCl at room temperature and contacted with solid AlCl heated to approximately 90 C. to entrain both SiCL, and AlCl
  • a stream of oxygen flows to the intermediate tube 11. This oxygen can be preheated in heater 2.
  • a stream of hydrogen entraining sodium vapors flows into the outer tube 12.
  • the gaseous mixture is ignited and burns at 4.
  • the products of reaction are collected on a cold rod 3 which is rotated in and moved endwise through the flame 4.
  • glasses may be obtained, for example, an ingot of transparent silica containing GeO with the following composition:
  • the GeCl is heated to about 100 C.
  • the GeCl is heated to about C.
  • the sodium metal vapors are entrained lay an hydrogen preheated stream.
  • the support must be chosen according to the glass to be obtained.
  • the support is a silica rod.
  • a method of preparing silica glass that corn-prises entraining a silicon halide in a current of chlorine, bringing the current together with currents of oxygen and hydrogen and igniting them, and condensing the glass formed on a cold surface.
  • the gas phase method of making glass which comprises forming concentric streams of chlorine, oxygen, and hydrogen with chlorine at the center and hydrogen as an exterior envelope, entraining silicon tetrachloride in the chlorine, igniting the concentricstreams, and collecting the glass formed thereby.
  • the gas phase method of making glass which comprises forming concentric streams of chlorine, oxygen, and hydrogen with chlorine at the center and hydrogen as an exterior envelope, entraining silicon tetrachloride in the chlorine, entraining an alkali metal in the hydrogen, igniting the concentric streams, and collecting the glass formed thereby.
  • a method of preparing a silica glass that comprises entraining a silicon halide in a current of chlorine gas, entraining an alkali metal in a current of hydrogen, bringing the currents together with a current of oxygen, igniting them and condensing the glass formed on a cold surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
  • Silicon Compounds (AREA)
US169763A 1961-02-02 1962-01-30 Manufacture of silica glass Expired - Lifetime US3334982A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR851475A FR1287541A (fr) 1961-02-02 1961-02-02 Perfectionnement à la fabrication de verres siliciques

Publications (1)

Publication Number Publication Date
US3334982A true US3334982A (en) 1967-08-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
US169763A Expired - Lifetime US3334982A (en) 1961-02-02 1962-01-30 Manufacture of silica glass

Country Status (3)

Country Link
US (1) US3334982A (fr)
FR (1) FR1287541A (fr)
GB (1) GB989467A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460926A (en) * 1967-07-17 1969-08-12 Owens Illinois Inc High silica content glasses
JPS4826208A (fr) * 1971-08-09 1973-04-06
JPS4873522A (fr) * 1972-01-03 1973-10-04
DE2364782A1 (de) * 1973-01-04 1974-07-11 Corning Glass Works Optischer wellenleiter
JPS4999709A (fr) * 1973-01-04 1974-09-20
JPS5430853A (en) * 1977-08-11 1979-03-07 Nippon Telegr & Teleph Corp <Ntt> Production of soot form glass rod
US20090211301A1 (en) * 2008-02-27 2009-08-27 Shin-Etsu Chemical Co., Ltd. Method of fabricating an optical fiber preform and a burner therefor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5429263B2 (fr) * 1974-01-14 1979-09-21
JPS6026055B2 (ja) * 1980-12-23 1985-06-21 東芝セラミツツクス株式会社 石英ガラスおよびその製造方法
DE3327484A1 (de) * 1983-07-29 1985-02-14 Siemens AG, 1000 Berlin und 8000 München Verfahren zur herstellung von glas durch abscheidung aus der gasphase

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2272342A (en) * 1934-08-27 1942-02-10 Corning Glass Works Method of making a transparent article of silica
US2798792A (en) * 1949-07-20 1957-07-09 Helsingborgs Gummifabriks Method for the production of finely divided silicon dioxide
US2967113A (en) * 1957-11-18 1961-01-03 Gen Electric Coating method
US3043660A (en) * 1958-03-10 1962-07-10 British Titan Products Production of silicon dioxide
US3128166A (en) * 1953-11-25 1964-04-07 Heraeus Schott Quarzschmelze Process for producing quartz glass

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2272342A (en) * 1934-08-27 1942-02-10 Corning Glass Works Method of making a transparent article of silica
US2798792A (en) * 1949-07-20 1957-07-09 Helsingborgs Gummifabriks Method for the production of finely divided silicon dioxide
US3128166A (en) * 1953-11-25 1964-04-07 Heraeus Schott Quarzschmelze Process for producing quartz glass
US2967113A (en) * 1957-11-18 1961-01-03 Gen Electric Coating method
US3043660A (en) * 1958-03-10 1962-07-10 British Titan Products Production of silicon dioxide

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460926A (en) * 1967-07-17 1969-08-12 Owens Illinois Inc High silica content glasses
JPS4826208A (fr) * 1971-08-09 1973-04-06
JPS4873522A (fr) * 1972-01-03 1973-10-04
DE2364782A1 (de) * 1973-01-04 1974-07-11 Corning Glass Works Optischer wellenleiter
JPS4999709A (fr) * 1973-01-04 1974-09-20
JPS5430853A (en) * 1977-08-11 1979-03-07 Nippon Telegr & Teleph Corp <Ntt> Production of soot form glass rod
US20090211301A1 (en) * 2008-02-27 2009-08-27 Shin-Etsu Chemical Co., Ltd. Method of fabricating an optical fiber preform and a burner therefor
US9260339B2 (en) 2008-02-27 2016-02-16 Shin-Etsu Chemical Co., Ltd. Method of fabricating an optical fiber preform and a burner therefor

Also Published As

Publication number Publication date
GB989467A (en) 1965-04-22
FR1287541A (fr) 1962-03-16

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